Anthraquinone compounds

ABSTRACT

WATER-SOLUBLE ANATHRAQUINONE DYES WHICH BEAR ONE OR TWO 3,5,5-TRIMETHYLCYCLOHEXYLAMINO GROUPS IN THE 1-AND/ OR 4-POSITIONS AND ONE OF TWO-SO3H GROUPS BOUND EITHER DIRECTLY TO A CARBON ATOM OF AN AROMATIC RING OR INDIRECTLY OVER AN OXYGEN ATOM TO A CARBON ATOM OF AN ALIPHATIC CHAIN.

United States Patent Oifice 3,646,071 ANTHRAQUINONE COMPOUNDS Wolfgang Frey, Munchenstein, Basel-Land, and Wolfgang Schoenauer, Riehen, Basel-Land, Switzerland, assignors to Sandoz Ltd., Basel, Switzerland N Drawing. Filed Mar. 18, 1969, Ser. No. 808,322 Claims priority, application Switzerland, Apr. 8, 1968,

5,122/68; May 31, 1968, 8,169/68; Sept. 30, 1968,

Int. Cl. C09b N30 US. Cl. 260-371 2 Claims ABSTRACT OF THE DISCLOSURE Water-soluble anathraquinone dyes which hear one or two 3,5,5-trimethylcyclohexylamino groups in the 1- and/ or 4-positions and one of two SO H groups bound either directly to a carbon atom of an aromatic ring or indirectly over an oxygen atom to a carbon atom of an aliphatic chain.

This invention relates to new anthraquinone compounds, the processes of their production and their uses. These anthraquinone compounds are of the formula A1NH CH3 CH3 where A represents one of the radicals O NH; O NH; H I ll R1 50311 R! XRz I l l 0 (II) 0 (III) (I? NH-R fl) IIIH-R,

7 B 01 HOgS-t/ II I II I 0 (IV) 0 In Formulae II or V one R stands for a hydrogen, fluorine, chlorine or bromine atom or a SO H-group and the other R for a hydrogen atom, or R in each instance stands for a chlorine atom,

SO H

R for secondary alkyl having 3 to 6 carbon atoms, cyclohexyl, 3,5,5-trimethylcyclohexyl, or

R for hydrogen, alkyl or alkoxy having 1 to 9 carbon atoms or halogen,

3,646,071 Patented Feb. 29, 1972 R1] for hydrogen or alkyl having 1 to 8 carbons atoms,

R12 for CHz-, CHz-CH:- or (!3H-,

X for-O- or S-, alkylene for CH2, -CH2CH2-, CH, CHzCH- or CHCH5,

( lHa CH3 CH3 m for 1 or 2, n for 1 to 3,

p for 1 to 9 and r for 1 to 6.

The 50 11 group in Formula V may be in the 6- or 7- position; the nucleus B may bear a chlorine atom or an SO H group in the 6- or 7-position or two hydroxyl or amino groups or one hydroxyl and one amino group in the 5- and 8-positions, respectively; the nucleus C may bear 1 to 3 lower alkyl or alkoxy groups; if n stands for 2 or 3, every substitutent R may have a separate significance.

The preferred compounds are those of the formulae Particularly valuable compounds of Formulae VII and VIII are those in which R stands for the radical of a sulphonated phenol which may hear an alkyl group in the para-position or for a sulphated Z-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl or 2,3-dihydroxypropyl radical,

R for a sulphonated benzene radical which may bear 1 to 3 lower alkyl groups, a lower alkoxy or acylamino group, or for a sulphonated benzyl or phenylalkyl radical, the radical in which is connected to the amino group through a secondary carbon atom, or for a radical of the formula -(OH C-N where m stands for 1 or 2,

R for hydrogen, methyl, or ethyl and R for hydrogen,

methyl, ethyl, chlorine, methoxy, ethoxy or acetylamino.

The new compounds are produced by reacting 1 mole of 3,5,S-tri-methylcyclohexylanfine with 1 mole of an anthraquinone compound of one of the formulae where Hal stands for chlorine, bromine or fluorine, Y for bromine or -SO H,

80 151 or -alkylene-OO R11 7 3 If Y represents bromine, the reaction product is treated with a water soluble neutral sulphite, or if R bears no SO H group, with sulphur trioxide or an agent yielding sulphur trioxide.

A variation of the process consists in reacting 1 mole of an anthraquinone compound of formula (1) Hal CH3 A iH CH CH (XII) with 1 mole of an amine of formula R NH and, if the radical R contains no SO H group, treating the product with sulphur trioxide or with an agent yielding sulphur trioxide.

A second variation of the process consists in reacting 1 mole of an anthraquinone compound of formula 0 NHg l l I (l NH CH CH (XIII) with a compound of one of the formulae HalR OH Hal-CH; and no-om-Q and treating the product with sulphur trioxide or an agent yielding sulphur trioxide; or reacting 1 mole of the aforesaid compound with 1 mole of an alkylenecarboxylic acid which has 3 or 4 carbon atoms and a double bond in the a-position or with a halogenoacetic acid or with a func tional derivative of these acids, and then reacting with an amine of formula Hal- (XIV) in the presence of an inorganic acid halogenide and treating the product with sulphur trioxide or an agent yielding sulphur trioxide.

A process for the production of anthraquinone compounds of the formula consists in reacting 1 mole of 1,4-dihydroxyanthraquinone-6- or -7-sulphonic acid with 1 mole of 3,5,S-trimethylcyclohexylamine and 1 mole of an amine of formula R -NH or reacting 1 mole of a compound of Formula XII in which the nucleus B bears a sulphonic acid group with 1 mole of an amino R -NH A process for the production of anthraquinone compounds of the formula consists in reacting 1 mole of an anthraquinone compound of Formula IX with 1 mole of 3,5,5-trimethylcyclohexylamine and reacting the product with 1 mole of a compound of one of the formulae and treating with sulphur trioxide and an agent yielding sulphur trioxide.

Examples of suitable compounds of Formula IX are 1- amino-2,4-dibromoanthraquinone, l-amino-4-bromo, 1- amino-4,6- and -4,7-dibromo, 1-amino-4-bromo-6-chloroand -7 chloro, l amino-4-bromo-6- and -7-fluoro-, lamino-4-bromo-6,7-dichloroanthraquinone 2 sulphonic acid, l-amino-4-bromoanthraquinone-2,6- and-2,7-disulphonic acid.

The following are examples of suitable compounds of Formula X: l-pheny1amino-4-bromoand -4-chloroanthraquinone, -4,6(7)-dichloro-, -4-bromo-6- and -7- chloroanthraquinone, -4-chloro-S,8-diamino-, -5,8-dihydroxy-, -5-amino-8-hydroxyor -5-hydroxy-8-aminoanthraquinone and -4-bromoanthraquinone-6- and -7-sulphonic acid and their derivatives, which bear in the phenyl nucleus alkyl or alkoxy radicals having 1 to 5 carbon atoms (methyl, ethyl, isopropyl, n-propyl, n-butyl, namyl, tert. butyl, isobutyl, methoxy, ethoxy, n-butoxy, dimethyl, trimethyl, methylethyl, methyl-methoxy, dimethoxy, diethoxy, diethyl), halogen atoms (chlorine, bromine, fluorine) or lower acylamino radicals, (acetylamino, propionylamino, n-butyrylamino, methoxycarbonylamino, ethoxycarbonylamino), as well as the corresponding compounds which are sulphonated in the substituted or unsubstituted phenyl radical; 1-(2-hydroxyethylamino)-, 1-(3'-hydroXypropyl-2-amino)-, 1-(2,3'- dihydroxypropylamino) 1- 4'-hydr0Xybutyl-3 '-amino 1-(4'-hydroxybutyl-2'-amin0)-4-chloroand -4-bromo chloro-, -4-bromo-6- and -7-chloro-anthraquinone, -4- chloro-5,8-diamino-, -5,8-dihydroXy-, S-amino 8 hydroXy-, -5-hydroxy8-aminoanthraquinone, -4-chloro and 4-bromo-anthraquinone-6- or -7-sulphonic acid and the corresponding compounds which are sulphated on the hydroxyalkyl group; l-benzylamino-l, 1-(4-pheny1-4'- methylpentyl-2'-amino) 1-(4-phenyl butyl-2'-amino)- and 1- 6'-phenyl-2-methyl-heXy1-4-amino -4-chloroand -4-bromo-anthraquinone, 4,6- or -4,7-dichloroor -4- bromo-6- or -7-chloroanthraquinone, -4-chloro-5,8-diamino-, -5,8-dihydroxy-, 5-amino-8-hydroxy-, -5-hydroxy 8-amino-anthraquinone, 4-chloroor -4-bromo-anthraquinone-6- or -7-sulphonic acid; l-(2-benzylcyclohexylamino)-, 1-(2'-;3-phenylethylcyclohexylamino)- 1-[2- (2- or 4-methylbenzyl)- and -ethyl benzyland -npropyl-benzyl)-eyclohexylamino]-, 1-[2'-(2-4"- or (2", 6"-dimethylbenzyl)- and -diethylbenzyl) cyclohexylamino]-, or 1-[2'-(2",4",6"-trimethylben2yl) cyclohexylamino]-, 1-[2-(2- and -4-methoxybenzyl)- or -ethoxybenzyl)- or -n-propoxybenzyl) cyclohexylamino]-, 1-[2-(2",4"-dimethoxybenzyl)- or -diethoxybenzyl)-cyclohexyl-amino]-, l-(2-benzyl-4-methyl-, -4- ethy1-, -4-tert.butyl-, -4'-tert.amyland -4'-isooctylcyclohexylamino)-4-chloroor -4-bromoanthraquinone, -4,6- and -4,7-dichloroand -4-bromo-6- or -7-chloro-anthraquinone, -4-chloro-5,8-diamino-, -5,8-dihydroXy-, -5- amino-8-hydroxy-, -5-hydroxy-8-amino anthraquinone and -4-chlor0- or -4-bromo-anthraquinone-6- and -7-sulphonic acid; as well as the corresponding compounds which are sulfonated in the aryl nucleus; 1-(2-phenylaminocarbonylethylamino) 1-(2-phenylaminocarbonylpropylamino)-, 1 (1' phenylaminocarbonylpropyl-2' amino)-, 1-phenylaminocarbonylmethylarnino-, l-(2-N- methyl N phenylaminocarbonylethylamino)-, 1-(2'-N- ethyl-N-phenylaminocarbonylethylamino)-, l-N-methyl- N-phenylaminocarbonylmethylamino-, 1 N ethyl-N- phenylaminocarbonylmethylamino 4 chloroand -4- bromo-, -4,6- or -4,7-dichloro-, -4-bromo-6,7-chloroanthraquinone, -4-chloro-5,8-diamino-, -5,8-dihydroxy-, -5-amino-8-hydroxy-, -S-hydroxy-8-amino-anthraquinone and -4-chloroand -4-bromo-anthraquinone-6, and -7- sulphonic acid and their derivatives which bear in the phenyl nucleus alkyl or alkoxy radicals having 1 to 5 carbon atoms (methyl, ethyl, isopropyl, n-propyl, nbutyl, n-amyl, tert.amyl, tert.butyl, isobutyl, methoxy, ethoxy, n-butoxy, dimethyl, trimethyl, methylethyl, methylmethoxy, dimethoxy, diethoxy, diethyl), halogen atoms (chlorine, bromine, fluorine) or lower acylamino radicals (acetylamino, propionylamino, n-butyrylamino, methoxycarbonylamino-, ethoxycarbonylamino), and the corresponding compounds which are sulphonated in the substituted or unsubstituted phenyl nucleus.

The compounds of Formula X can be produced by reacting 1 mole of a compound of the formula 0 Hal H I H 0 Hal (XVII) with 1 mole of an amine R NH or by halogenation of a compound of the formula g (XVIII) The compounds of Formula X, in which R represents a radical of the formula (Ron -alkylene-CON 8) -alkylene-C0-N can be obtained by reacting 1 mole of a compound of Formula XVII with 1 mole of an aminocarboxylic acid H N-alky1ene-COOH and reacting with an amine of Formula XIV in the presence of an inorganic acid halogenide or alternatively reacting with an amine of Formula XIV with subsequent sulphonation. Another mode of operation consists in reacting 1 mole of a compound of the formula I O NHz y) lital (XIX) with 1 mole of an alkylenecarboxylic acid which has 3 or 4 carbon atoms and a double bond in the a-position, or with 1 mole of a halogenoacetic acid or a functional derivative of one of these acids, after which the product is reacted with an amine of Formula XIV in the presence of an inorganic acid halogenide or reacted with an amine of Formula XIV and sulphonated.

Examples of suitable compounds of Formula XI are lisopropy1, l-sec. butyl-, l-sec. amyl-, l-sec. hexyl-, l-cyclohexylamino-and 1 (3,5',5-trimethylcyclohexylamino)-4-chloroor 4-bromoanthraquinone-6- or -7-sulphonic acid. They can be prepared by reacting 1 mole of 1,4-dihalogenoanthraquinone-6- or -7-sulphonic acid with 1 mole of an amine R -NH or by halogenation, preferably bromination, of a l-R -NHanthraquinone-6- or -7-sulphonic acid.

The reaction of the 3,5,5-trimethylcyclohexylamine with the compounds of Formulae IX, X or XI can be effected at temperatures ranging from 40 to 220 C. The water soluble anthraquinone compounds are best reacted in an aqueous or aqueous-organic medium, e.g. at temperatures of 45 to 100 C., or preferably 45 to 85 C. for the compounds of Formula IX in which Y stands for SO H, while the water insoluble anthraquinone compounds are best reacted in organic medium, e.g. 80 to 200 C. or preferably, 100 to 150 C., more particularly 110130 C., for the compounds of Formula IX where Y stands for a bromine atom. Mixtures of Water and one or more solvents which are at least partially water-soluble and are indifferent to the reactants are employed as aqueous-organic media, e.g. lower alcohols (methanol, ethanol, isopropanol, butanol, ethylene glycol), ethers (dioxan, 1,2 dimethoxyor 1,2-diethoxyethane), ether alcohols (2-methoxyor 2-ethoxyethanol, 2-(2-methoxyethoxy)- or 2-(2'-ethoxyethoxy)-ethanol), ketones (methylethyl ketone), amides (dimethylformamide, dimethylacetamide), sulphoxides and sulphones (dirnethylsulphoxide, sulpholan-tetramethylenesulphone). These solvents are used in amounts of up to 25% or preferably to on the total weight of the mixture.

It is of advantage to react in the presence of acidbinding agents which impart to the reaction medium a pH of at least 11 (the pH value of a saturated aqueous solution of 3,5,5-trimethylcyclohexylamine) and of a catalyst; for this purpose preference is given to alkali metal hydroxides (sodium or potassium hydroxide) and to copper catalysts (copper powder, copper-I-oxide, copper-I- chloride, copper-II-oxide). To accelerate the reaction, it is desirable to employ an excess of 3,5,5-trimethylcyclohexylamine, e.g. 1.3 to 3 moles or, prefer-ably, 1.5 to 2 moles, per mole of the halogenanthraquinone compound.

For the reaction in organic medium the 3,5,5-trimethylcyclohexylamine itself is employed as solvent or a solvent is used which is indifferent to the 3,5,5-trimethylcyclohexylamine and of high boiling point, e.g. 130 to 220 C., for example monoor di-chlorobenzene, dimethylformamide, dimethylacetamide, dimethylsulphoxide, glycol ethers and in particular, nitrobenzene. Examples of suitable acid binding agents are an excess of the amine, a tertiary amine of low volatility and of higher basicity than 3,5,5 trimethylcyclohexylamine, a basic metal salt, such as sodium or potassium carbonate, or an alkali metal hydroxide. If necessary the aforenamed copper catalysts are employed.

The final products are isolated in the normal way, e.g. by evaporation, preferably at reduced pressure, water vapour distillation, or dilution with a suitable agent, eg. with water when water soluble solvents are used, or with a lower alcohol, such as methanol, ethanol or isopropanol, or a hydrocarbon, such as petroleum ether or ligroin. On isolation they are filtered with suction, washed if necessary and dried.

After condensation of the 3,5,5-trimethylcyclohexylamine with a compound of Formula IX in which Y stands for a bromine atom the reaction product is reacted with a neutral, water soluble sulphite in aqueous-organic, e.g. aqueous-alcoholic or aqueous-phenolic (phenol itself, a cresol or cresol mixture) medium, in which the concentrated sulphite solution forms the aqueous phase, at to 150 0., preferably 130 C. under pressure.

If the compounds of Formula X in which R represents an aralkyl radical or a cyclohexyl radical are acylated prior to condensation with 3,5,5-trirnethylcyclohexylamine, the rate of reaction is greatly accelerated so that the temperature can be reduced to, e.g., 60 130 C. or, preferably, 80l00 C., when the amine itself is used as solvent, and/or the reaction time is shortened or the formation or by-products can be greatly reduced. Examples of suitable acylating agents are lower alkanesulphonic acid chlorides (methaneand ethanesulphonic acid chlorides), arenesulphonic acid chlorides (benzene or 4-methylbenzenesulphonic acid chlorides), chlorocarbonic acid alkyl esters (chlorocarbonic acid methyl or ethyl esters) and in particular lower carboxylic acid chlorides and anhydrides (propionic acid chloride and anhydride or preferably acetic acid chloride or anhydride). The acetyl compound can be formed by adding the anthraquinone compound to five to ten times its amount of acetic anhydride containing 2-5 zinc chloride on the weight of the anthraquinone compound, raising the mixture from 60 to about -140 C. or preferably, 80l00 C. and holding it at this temperature until the starting compound has disappeared, on which the mixture is cooled, run into water, the excess acetic anhydride carefully saponified and the precipitated product suctioned off, washed with water, dried and if neces sary recrystallized in 100% acetic acid or in an alcohol.

After condensation with the 3,5,S-trimethylcyclohexylamine the acyl group is split off, e.g., by treatment in 55-80% or preferably 60-65% sulphuric acid at 5080 C. or preferably, 6040".

The reaction of the anthraquinone compounds of Formula XII with an amine R NH can be accomplished under the aforestated reaction conditions. Here again prior acylation of the trimethylcyc'lohexylamino group accelerates the rate of reaction, given a substantial excess of the unsulphonated amine.

If the reaction is conducted in an organic medium, an alkali metal acetate, carbonate or hydroxide can be employed for an aromatic amine, depending on the strength of the amine, or an alkali metal carbonate or hydroxide for an amine of different type.

If the anthraquinone compound (XII) bears an -SO H group in the 6- or 7-position, it is advisable to react in aqueous or aqueous-organic medium in the presence of an acid-binding agent, e.g. an alkaline metal acetate, bicarbonate, carbonate or hydroxide when an aromatic amine is employed, or an alkali metal hydroxide in the case of an aromatic-aliphatic amine.

Suitable amines R -NH include aminobenzene, 1- amino-2-, -3- or -4-methyl-, -ethylor -isopropylbenzene, 1-amino-2,4-, -2,5- or -2,6-dimethylor -diethylbenzene, 1-amino-2,4,6- or -2,4,5-trimethylbenzene, l-amino-Z- methyl-4,6-diethylbenzene, 1-amino-4-n-butyl-, -4-isobutyl-, -4-tert-butyl-, -4-tert-amyl-, -4-n-amyl-, -4-isooctyl-, -4-tert-octylbenzene, 1-amino-2-, -3- or -4-chloroor -bromobenzene, 1-amino-2,4-dichlorobenzene, l-amino- 2-, -3- or -4-methoxyor -ethoxybenzene, 1-amino-2,4- dimethoxyor -diethoxybenzene, l-amino-2,5-dimethoxyor -diethoxybenzene, l-amino-Z-methoxy-S-methylben- Zene, l-amino-4-acetylamino-, -propiony.lamino-, -butyry-lamino-, -methoxycarbonylaminoor -ethoxycarbonylaminobenzene, or the monosulphonic acids of these aminobenzenes corresponding to the formulae (Rah ah H: 6 ans HzN-Q 2 hydroxy ethylamine, 2 hydroxypropylamine 1; 3- hydroxypropylamine 1; 1 hydroxypropylamine 2-, 1 hydroxybutylamine 3, 1 hydroxybutylamine 2, 2,3 dihydroxypropylamine 1 or their sulphuric acid esters corresponding to the formulae benzylamine, 2 amino 4 methyl 4 phenylpentane, 2 amino 4 phenylbutane, 4 amino 2 methyl 6- phenylhexane or their monosulphonic acids corresponding to the formulae PEN-R100 01 PEN-H O mulae I and aminoacetic acid-, u-arninoor fi-aminopropionic acid-, a-aminomethylpropionic acidand [i-amino-butyric acidphenylamide, N-methylor N-ethyl-N-phenylamide, (2'-, -3- or -4'-methyl-, -methoxy-, ethoxyor chlorophenylamide)-, -(2',4-, -2',5- or -2,6'-dimethylphenylamide), (2,4,6'- or -'(2',4',5 trimeth'ylphenylamide), -(4'-ethyl-, -(4-isopropyl, -(4'-n-butyl-, (4'-isobutyl-, -(4'-tert-butyl-, -4'-n-amyl-, -(4'-isoamyl-, -(4'-tert-amyl-, -(4-isooctyl or (4'-tert-octylphenylamide), -(4'-bromophenylamide, -(2',5 dichlor0-, -(2',5' dimethoxyor -(2',5 '-diethoxy-phenylamide) -(2'-methoxy-5-methylphenylamide), -(4-acetylamino-, -(4'-propionylamino- -(4-butyrylamino-, -(4-methoxycarbonylaminoor -(4 ethoxycarbonyl-arninophenylamide) or their monosulphonic acids corresponding to the formulae (Rah The reaction of the anthraquinone compounds of Formula XIII with a compound Hal-R OH or Hal-CH Halcan be conducted in a substantial excess of the halogen compound or in a polar solvent, such as dimethylformamide, dimethylsulphoxide or, preferably, nitrobenzene at 90 to 200 C., preferably 130-180 C. or more particularly 135-150 C. for the aryl halides, preferably 80- 130 C. or in particular 1001l0 C. for the benzyl halides, and 80-130 C. for the hydroxyalkylhalides, and in the presence of an acid-binding agent, such as 10 alkali metal acetate, carbonate, bicarbonate or hydroxide, and of a copper catalyst (copper powder, copper-I-oxide or copper-I-chloride).

The compounds of Formula XIII can be produced by condensation of bromamic acid or its derivatives with 3,5,5 trimethylcyclohexylamine and desulphonation, or by reaction of 1 mole of a dihalogen compound of Formula XVII in either sequence with 1 mole of 3,5,5-trimethylcyclohexylamine and 1 mole of ammonia or of an aliphatic or aromatic sulphonic acid amide in the latter case with subsequent cleavage of the sulphonic acid radicals.

Amongst the halogen compounds suitable for reaction with aminoanthraquinone compounds of Formula XIII may be mentioned bromobenzene, 1,2-, 1,3- and 1,4- dibromobenzene, 1 bromo-2-, -3-, and 4-methy1- and ethylbenzene, 1-bromo-2-, 3- and -4'-chlorobenzene, lbromo-2-, 3- and 4 methoxyor ethoxybenzene, 1- bromo 2,4,6 trimethylbenzene, 1-bromo-2-methoxy-5- methylbenzene, l-bromo-4-is0propyl-, -4-n-butyl-, 4-tertbutylbenzene, 1 bromo-4-acetylamino-, 4-propionylaminoand 4-butyrylaminobenzene, corresponding to the formula Hal 2-chl0roor 2-bromethanol, 2-chloroor 2-bromopropanol-l, l-chloro or 1-bromo-2-propanol, 3-chloroor 3- bromopropanol, l-chloroor l-bromo-2,3-propanediol, corresponding to the formula HalR OH; benzyl chloride or benzyl bromide corresponding to the formula It is of advantage to react the aminoanthraquinone compounds of Formula XIII with benzyl alcohol in a substantial excess of the alcohol within the temperature range of to 130 C. or preferably 110 C. and in the presence of iodine as catalyst, the amount of iodine being about 3 to 15% or, preferably, 8l2% of the aminoanthraquinone compound.

The reaction of aminoanthraquinone compounds of Formula XIII with alkylenecarboxylic acids having 3 or 4 carbon atoms and a double bond in a-position, or with functional derivatives of these acids, e.g. acrylic acid, acrylic acid ester, amide, or nitrile, methacrylic acid, methacrylic acid ester or crotonic acid, can be conveniently effected in sulphuric acid solution using sulphuric acid preferably of 50% to 96% strength.

The reaction takes place at temperatures between 40 and 100 C. or preferably at 60-80' C. The amount of alkylenecarboxylic acid employed must be at least 1 mole. It is often of advantage to employ an excess of the alkylenecarboxylic acid in order to achieve good yields. The addition of a further acid, e.g. concentrated phosphoric acid, can accelerate the reaction. In the course of the reaction the functional derivatives are often hydrolysed to the free acids. Should this not be so, hydrolysis is carried out subsequent to the reaction.

The reaction products can be isolated as described in British Pat. 841,927.

The reaction of aminoanthraquinone compounds of Formula XIII with a halogenoacetic acid can be accomplished in melted bromacetic or chloracetic acid, if desired in the presence of an alkali metal acetate and a copper compound, at temperatures of 60 to C. or, optimally, at 80-90 C., or in an inert organic solvent, such as phenol, a cresol or cresol mixture or naphtha in the presence of an alkali metal acetate and a copper compound at temperatures of 100 to C. or, preferably, 100120 C. To isolate the product it is best to distill 1 1 01f the solvent, e.g., with water vapour or under reduced pressure; the product is then precipitated by the addition of salt or acid, filtered off with suction and purified in the normal manner.

For amidation the dry carboxylic acids thus obtained are reacted with an amine of Formula XIV in the presence of a halide of an acid (thionyl chloride, phosphorus oxychloride, phosphorus pentachloride, phosphorus pentabromide, or preferably phosphorus trichloride or tribromide) and in an inert organic solvent, e.g. a halogenated or unhalogenated hydrocarbon, such as chloroform, carbon tetrachloride, benzene, toluene, Xylene, ch10- robenzene, dichlorobenzene, or in an ether, such as dioxane,1,2-dimethoxyor 1,2-diethoxyethane, di-isopropyl-, di-n-propylether or in a tertiary amine, such as pyridine, a mixture of pyridine bases, quinoline, dimethylaminobenzene or diethylaminobenzene. In place of an inert organic solvent the amine of Formula XIV itself can be employed as solvent. The reaction is eifected at temperatures between and 50 C. in the presence of one of the aforenamed acid halides and is brought to a close at temperatures of 0 to 100 C. or, preferably, 40 to 80 C. The resulting carboxylic acid phenylamides can be isolated in the normal way as described in the examples of British Pat. 1,061,424.

The reaction of 1,4 dihydroxyanthraquinone 6-sulphonic acid with 1 mole of 3,5,5-trimethylcyclohexylamine and 1 mole of an amine R NH can be carried out at temperatures of 50 to 150 C. or preferably at 80-120 C. By the addition of boron compounds (boric acid, boron trifluoride) and/or by employing the 1,4-dihydroxyanthraquinone-6-sulphonic acid wholly or partially in the form of the leuco compound, the introduction of a second 3,5,S-trimethylcyclohexylamino group can be appreciably accelerated. The reaction can be effected in a substantial excess of 3,5,5-trimethylcyclohexylamine or, particularly when condensation with two different amines is involved, in an inert organic solvent, e.g. an alcohol, such as ethanol, n-propanol, nor isobutanol, nor iso-amyl alcohol, a glycol, such as ethylene glycol, 1,2-propylene glycol, diethylene glycol, dipropylene glycol or tripropylene glycol an ether alcohol, such as 2-methoxy-, 2-ethoxyor Z-n-butoxyethanol, 2-(2'- methoxy-, -ethoxyor -n-butoxy-ethoxy)-ethanol or in an ether, such as dioxane, and if necessary with the addition of up to 30% water. After the condensation reaction, which takes place preferably in the absence of air, e.g. in a nitrogen or illuminating gas atmosphere, the leuco compound is reoxidized, e.g. by the introduction of air.

The reaction product of the formula 0 NH, ll

It, cu,

NH- r1 ctr om xx prepared from 3,5,5-trimethylcyclohexylamine and a compound of Formula IX, is reacted with hydroxy or thiol compounds of one of the formulae at temperatures of e.g., 50 to 200 C., preferably at 50 to 150 C. or optimally at 60 to 120 C. in the case of the thiol compounds, and 100 to 200 C. or more particularly, 110 to 180 C. in the case of the hydroxyl compounds, and in the presence of acid-binding agents, such as alkali metal carbonates or hydroxides. It is advantageous to react in an inert solvent, e.g. an alcohol, such as ethanol, =butanol, cyclohexanol an ether alcohol, such as 2-methoxy-, 2'ethoxyor Z-butoxyethanol, 2-(2'- methoxy-, 2-(2'-ethoxyor 2-(2-butoxy-ethoxy)-ethanol; an ether, such as dioxane; or in a hydrocarbon, such as cyclohexane, toluene or chlorobenzene or, if the compounds of Formula IX bear a sulphonic acid group, in water in the case of thiol compounds. An excess of the thiol compound may be employed as solvent. Suitable solvents for the reaction with hydroxy compounds include pyridine, a mixture of pyridine bases, quinoline, nitro benzene, 2,6-di-tert. butyl-4-methylphenol, or an excess of the hydroxy compound itself. Any water present or formed prior to or during the reaction is eliminated. For the reaction of the bromine atom in the 2-position it may be of advantage to add a copper catalyst, e.g. copper-I- chloride, especially in the case of thiol compounds. The reaction products are precipitated in the known way, e.g. by dilution with a lower alcohol or, if water-soluble or alkali-soluble hydroxyl or thiol compounds have been employed, with water or with alkali hydroxide solutions, and then filtered olf with suction, washed and dried.

The treatment with sulphur trioxide (in gaseous form diluted with air or as an adduct on pyridine or dioxane, or with chlorosulphonic acid) can be carried out in an inert solvent, such as chloroform, 1,2-dichlorethane or nitrobenzene, at temperatures of 0 to 50 C. or, preferably, at 15 30 C. Normally, however, concentrated sulphuric acid of about 96-100% strength is employed, or oleum with an S0 content of up to about 15% for reaction at the aforestated temperatures. Under these conditions the benezene nuclei are sulphonated and the aliphatic hydroxyl groups sulphated. For sulphation concentrated sulphuric acid can be employed at 10-20 C., whilst for sulphonation at the same temperature it is advisable to employ oleum with an S0 content of 5-10%. For converting the hydroxyalkyl groups into sulphatoalkyl groups, aminosulphonic acid can also be employed with advantage, e.g. at 100150 C. The sulphonated or sulphated compound can be isolated by running the solutions into water or into a salt solution, with the further addition of salt if necessary.

The final compounds are water-soluble dyes containing at least one SO H group and are employed for the exhaustion dyeing, pad dyeing and printing of wool, silk, hair fibres, polyamide and polyurethane fibres and leather. The dyeings and prints obtained on these materials are of brilliant shade and have good to very good wet fastness properties (washing, milling, perspiration, water, sea water), with good rubbing and dry cleaning fastness. On polyamide fibres the light fastness is very good and better than on wool.

In the examples the parts and percentages are by weight and the temperatures in degrees centigrade.

EXAMPLE 1 A mixture of 400 parts of water, 40.4 parts of sodium 1-amino-4-bromanthraquinone-Z-sulphonate, 20 parts of 1-arnino-3,5,S-trimethylcyclohexane, 15 parts of 30% sodium hydroxide solution, 50 parts of ethanol and 1 part of copper powder is stirred for 5 hours at 65. The blue dye formed is isolated and dried in the normal way. It is of Formula VI. From aqueous solution it gives dyeings of brilliant reddish blue shade on polyamide fibres which have very good wet fastness properties and outstandingly good light fastness.

This new dye has far better wet fastness properties on synthetic polyamide fibres than the known commercial dye which bears an unsubstituted cyclohexylamino group in the 4-position.

The same dye can be obtained by the following alternative route. A mixture of 38.1 parts of 1-amino-2,4-dibromanthraquinone, 160 parts of 3,5,5-trimethylcyclohexylamine, 25 parts of anhydrous potassium acetate and 0.5 part of copper-I-chloride is maintained at l20 until the starting material has disappeared. The mixture is then diluted with methanol and allowed to cool to room temperature. The precipitate is filtered off, washed successively with methanol and water and dried. It may be recrystallized if desired, after which 10 parts are mixed with 50 parts of phenol and 20 parts of 50% potassium sulphite solution in an autoclave and reacted at 130 for 16 hours. The phenol is distilled off with water vapour and the dye salted out, filtered off with suction and washed with salt solution. If necessary it is then dissolved in hot water, filtered while hot to free it from water-insoluble impurities and salted out, on which it is dried.

Dyeing example A solution of 2 parts of the dye of Example 1 in 6000 parts of Water at 40 is prepared and to it is added 4 parts of ammonium sulphate. 100 parts of a nylon 66 yarn are entered into the dyebath, which is then brought to the boil in 30 minutes and held at this temperature for 1 hour. Subseqeuntly the yarn is rinsed and dried. It is dyed in a fast, brilliant reddish blue shade.

The following Table 1 details further dyes of the which are specified by the substituents R present in the 6 and 7 positions and by the shade of the dyeings on wool or synthetic polyamide fibres.

TABLE 1 R in position 6 R in position 7 Shade of dyeings H Reddish blue. C1 D0. H D0. H D0. 6 SO3H H Blue. 7 1 Cl Reddish blue.

EXAMPLE 8 46.4 Parts of the sodium salt of the dye of Example 1 are dissolved in 600 parts of water at 60, with the addition of 46.5 parts of 30% sodium hydroxide solution. Over 1 hour 19 parts of sodium dithionite are sprinkled into the solution. After a further hour at 60 the desulphonation reaction is complete. The water-insoluble compound is filtered off, washed with hot water until of neutral reaction and dried. It is a dark violet powder which on recrystallization from toluene melts at 204205. It has the formula II 0 NH H on3 on (XXII) A mixture of 36.2 parts of the 1-arnino-4-(3',5',5-trimethylcyclohexamino)-anthraquinone thus prepared, 75 parts of bromobenzene, 15 parts of anhydrous sodium carbonate and 2 parts of cuprous chloride is reacted at 135140 for 4 hours. On cooling to 100, the mixture is diluted with 150 parts of ethyl alcohol, causing precipitation of the blue dye formed. This is filtered off, washed with ethyl alcohol and water and dried. It has the structure:

(XX II and its melting point (subseqoent to recrystallization from toluene and ethyl alcohol) is at 183 184. This water insoluble dye can be sulphonated in the benzene nucleus by normal methods, e.g. by treatment with five times its amount of 10% oleum at 5-10. Sulphonation yields a blue Water soluble dye which gives dyeings of an attractive blue shade on wool and synthetic polyamide fibres having excellent light and wet fastness properties.

By employing in place of bromobenzene the equivalent amount of 4-ethoxy-1-bromobenzene, a dye base with melting point 191 192 is obtained. The sulphonated derivative of this gives brilliant greenish blue dyeings on synthetic polyamide fibres which have excellent light and very good wet fastness properties (Washing, milling, perspiration, Water, sea water), together with very good rubbing and dry cleaning fastness. This dye is of greater brilliance and is faster to Washing and perspiration than the analogous dye bearing a cyclohexylamino group.

When other bromobenzenes are employed, the results are as follows:

TABLE 2 Shade of aque- Melting ous solution Exampoint of of the P dye base sulphonated N 0 Bromobeuzene (degrees) derivative l-bromo bmethylbenzene 174-175 Blue. 10. 1-br0m0-2,4-dimethylbenzene 178-179 Reddish blue. l-bormo-ZA,G-trimethylbenzene D 0.

EXAMPLE 12 It has the formula O3\CH3 (XXIV) 45.2 parts of this dye base are dissolved in parts of 100% sulphuric acid and 80 parts of 25% oleum at 5 8. The sulphonation reaction runs its course in 6 hours, fol lowing which the mixture is run into a mixture of parts of water, 400 parts of 28% aqueous sodium chloride 15 solution and 250 parts of ice. The dye settles out. It is filtered ofi, washed with 10% sodium chloride solution and dried at 100. The dye thus formed dyes synthetic polyamide fibres in brilliant blue shades which are fast to light and wet treatments.

The dyeings are faster to wet tests than comparable dyeings of the dye containing an unsubstituted cyclohexylamino group.

EXAMPLE 13 72.4 parts of 1-amino-4-(3,5,5'-trimethylcyclohexylamino)-anthraquinone are dissolved in 160 parts of benzyl chloride at room temperature, and after the addition of 18 parts of sodium bicarbonate the temperature is increased to 100. The condensation reaction takes 10 hours. After this time the mixture is cooled to 60 and the dye base precipitated with 300 parts of isopropyl alcohol. On sulphonation a dye identical with that of Example 12 is obtained.

EXAMPLE 14 3 6.2 parts of 1 amino 4-(3',5,5'-trimethylcyclohexylamino)anthraquinone are dissolved at 70 in a mixture of 90 parts of 55% sulphuric acid and 14 parts of acrylic acid, and the solution is stirred for a further 4 hours at this temperature. It is then run into 500 parts of water at 60. The crystalline precipitate is filtered E and washed with hot water until the waste Water runs virtually colourless and is of almost neutral reaction, on which it is dried at 100.

43.4 parts of 1- (2'-carboxyethylamino)-4-(3,5",5"- trimethylcyclohexylamino) -anthraquinone are dissolved in 150 parts of aniline at room temperature. 14 parts of phosphorus trichloride are dropped in at 40. Subsequently the temperature of the reaction mixture is increased to 60 and it is held at 6065 for 4 hours, after which time 160 parts of methyl alcohol are added which causes the dye base to settle out in crystalline form. It is filtered off, washed with methyl alcohol and then with water and dried at 100. The blue crystalline product is of the formula IIIHCHzCH CONHO CH CH (XXV) 50.9 parts of this dye base are dissolved at 16 in 100 parts of 100% sulphuric acid and 60 parts of 25% oleum. Sulphonation is complete in 5 hours. The solution is then run into a mixture of 150 parts of Water, 400 parts of 28% aqueous sodium chloride solution and 250 parts of ice. The dye settles out and is filtered off, washed with sodium chloride solution and dried at 100. A brilliant blue dye is obtained which gives dyeings of high light and wet fastness on synthetic polyamide fibres.

The acrylic acid employed in this example can be replaced by the equivalent amount of Z-methylacrylic acid, in which case it is preferable to carry out the reaction in 96% sulphuric acid at 95 1 00 in the presence of 3-5% of 100% phosphoric acid.

EXAMPLE A mixture of 23.1 parts of 1-(4-methyl-4'-phenylpentyl- 2-amino)-4-bromoanthraquinone, 0.1 part of copper powder and 42 parts of 3,5,5-trimethylcyclohexyla-mine is reacted at 80-85 for 48 hours with stirring. On cooling to 60, 120 parts of methanol are added dropwise. The

16 precipitate formed is filtered off at 2025, washed with methanol and dried. It is of the formula CH3 CH3 (Ill) lTIH(iiHCH a H l O NH H CH CH (XXVI) 10 parts of this dye base are dissolved in 40 parts of 100% sulphuric acid at 25 and the solution is stirred until no further starting material is present. It is then discharged onto ice and the precipitate thus formed is filtered off, washed with 10% sodium chloride solution and dried. A blue powder is obtained which dyes wool and synthetic polyamide fibres in brilliant greenish blue shades which have good light and wet fastness properties.

EXAMPLE 1 42.7 Parts of l-(3,3',5-trimethylcyclohexylamino)- anthraquinone-6-sulphonic acid are dissolved at 2025 in 220 parts of 100% sulphuric acid, with the addition of 16 parts of bromine. The temperature is slowly increased to and this temperature held for about 16 hours. On cooling, the reaction mixture is run onto 650 parts of ice. The precipitated 1-(3',3',5-trimethylcyclohexylamino)-4bromanthraquinone-6-sulphuric acid is filtered off, washed with water until of neutral reaction and dried.

25.3 Parts of this compound are suspended in 300 parts of water, on which 15 parts of 30% sodium hydroxide solution, 1 part of copper-I-chloride, 20 parts of isopropyl alcohol and 15 parts of 3,5,S-trimethylcyclohexylamine are added. The mixture is maintained at 65-70 until the starting compound has disappeared. It is then run into a mixture of parts of water and 15 parts of 30% hydrochloric acid to form a suspension. This is raised to 80 and the reaction product is filtered at this temperature and washed with acidified Water. It is then suspended in 500 parts of water, the suspension raised to 0 80 and neutralised with sodium carbonate, then the final dye is salted out and isolated.

The 15 parts of 3,5,5-trimethylcyclohexylamine can be replaced by 10 parts of cyclohexylamine or 6 parts of isopropylamine, in which case the reaction can be efiected without isopropyl alcohol. The dyes thus obtained give brilliant dyeings of good light and Wet fastness on synthetic polyamide fibres.

An aromatic amine, eg 9 parts of aminobenzene or 14 parts of l-amino-4-acetylarninobenzene, can be employed for the condensation reaction, in which case 9 parts of sodium carbonate are used as acid-binding agent and the isopropyl alcohol omitted. The resulting dyes give brilliant blue shades of high light and wet fastness on synthetic polyamide fibres.

This same condensation reaction can be carried out with 18 parts of sodium l-aminobenzene-3-sulphonate to give a wool dye.

The 1-(3,5,5' trimethylcyclohexylamino)-anthraquinone-6-sulphonic acid employed in the foregoing as starting product is prepared as follows.

A mixture of 108 parts of sodium anthraquinone-1,6- disulphonate, 50 parts of 3,5,S-trimethylcyclohexylamine, 40 parts of sodium 3-nitrobenzenesulphonate and 1.5 parts of copper sulphate in 360 parts of water is reacted in an autoclave for 36 hours at On cooling, the sodium salt of the l-(3',5',5'-trimethylcyclohexylamino)- anthraquinone-6-sulphonic acid is salted out, filtered off with suction and washed with sodium chloride solution until the filtrate runs colourless. The filter residue is dissolved in 3600 parts of water at 70, the solution 17 acidified with hydrochloric acid (red to Congo paper) and the product then filtered off, washed with acidified Water until the waste water runs colourless, and dried. The 1 (3,5',5' trimethylcyclohexylamino)-anthraquinone-6-sulphonic acid is obtained in the form of red crystals.

EXAMPLE 17 173.5 Parts (0.5 mole) of 1-(3',5',5'-trimethylcyclohexylamino)-anthraquinone are brominated in the 4- position by the method given in Example 16. 42.7 Parts of the resulting 1-(3',5,5'-trimethylcyclohexylamino)-4- bromanthraquinone are entered into 250 parts of acetic anhydride. After the addition of 2 parts of anhydrous zinc chloride the mixture is raised to 90100 and held at this temperature until the starting compound has disappeared. On cooling, the mixture is poured slowly into 1000 parts of water with vigorous stirring.

The temperature is kept below 30 by external cooling, and stirring is continued until the acetic anhydride is completely saponified to acetic acid. At this point the precipitated product is filtered off with suction, washed with water and dried.

23.5 Parts of the 1-(N-acetyl-N-3',5,5'-trimethylcyclohexylamino) -4-bromanthraquinone thus obtained are added to 19 parts of 1-phenyl-3-aminobutane and the mixture is reacted for 20 hours at 110 with stirring. It is then run into a mixture of 200 parts of ice, 170 parts of water and 30 parts of 30% hydrochloric acid. The precipitated resinous compound is separated and entered in portions into 175 parts of 65% sulphuric acid. The hydrolyzing mixture is maintained at 6070 until the red acyl compound is no longer indicated, on which it is run onto ice. The blue dye base can be recrystallized in n-butanol if desired and is then sulphonated with -10% oleum at 30. The dye thus obtained gives blue dyeings of good light and wet fastness on synthetic polyamide fibres.

The 1-(3',5',5' trimethylcyclohexylamino)-anthraquinone can be prepared as follows. A mixture of 242.5 parts (1 mole) of l-chloranthraquinone and 1000 parts of 3,5,5-trimethylcyclohexylamine is reacted at 100 until no further l-chloranthraquinone is indicated. The excess amine is driven off with water vapour and the residue introduced into 1000 parts of water with the addition of sufiicient concentrated hydrochloric acid to render the solution strongly acid. After stirring at 80, the product is filtered off with suction, washed with water until neutral and dried.

EXAM-PLE 18 A mixture of 21.4 parts of 1-(3,5,5-trimethylcyclohexylamino)-4-bromanthraquinone, 20 parts of l-phenyl- 3-aminobutane, 5 parts of anhydrous potassium acetate, 0.1 part of copper-I-chloride, 0.1 part of water and 3 parts of 2-ethoxyethanol is reacted at 110 for 48 hours with stirring. After the addition of 60 parts of n-butanol the mixture is allowed to cool. The dye base is then filtered off with suction, Washed with butanol and then methanol, recrystallized in n-butanol and dried. The sulphonated product is identical with the dye of Example 17.

The 1-(3',5',5 trimethylcyclohexylamino-4-bromanthraquinone can be replaced by 1-(3',5',5-trimethylcyclohexylamino)-4-chloranthraquinone, prepared by chlorination of 1-(3',5',5-trimethylcyclohexylamino)-anthraquinone with sulphuryl chloride in nitrobenzene with which the same dye is obtained.

EXAMPLE 19 '10 parts of 1-cyclohexylamino-4-bromanthraquinone-6- sulphonic acid are entered into a mixture of 200 parts of water, 20 parts of ethyl alcohol, 20 parts of 3,5,5-trimethylcyclohexylamine, 0.5 part of copper bronze and 7 parts of sodium hydroxide solution. The reaction mixture is maintained at 6070 until no further starting material is present. The resulting compound is worked up as described in Example 16 to give a dye which is isomeric to the dye referred to in the third paragraph of Example 16 and has properties very similar to it.

The use of 1-phenylamino-4-bromanthraquinone-6-su1- phonic in place of 1-cyclohexylamino-4-bromanthraquinone-6-sulphonic acid results in a similar dye.

EXAMPLE 20 A mixture of 23.5 parts of 1-(N-acetyl-N-3,5',5'-trimethylcyclohexylamino)-4-bromanthraquinone, 0.01 part of copepr-I-oxide, 5 parts of potassium acetate, 17.8 parts of Z-amino-l-butano'l and 50 parts of n-butanol is reacted for 24 hours at 115 C. with stirring. After the addition of 75 parts of methanol at 60 the temperature is allowed to fall to 2025. The product settles out and is filtered off, washed with methanol and dried. 20 parts of the product are dissolved in 100 parts of sulphuric acid and the solution is stirred at 60 for 8 hours, after which it is discharged onto ice. The precipitated dye base is filtered off, Washed neutral with water and dried at 60. 10 parts of this dye base are sulphated in 40 parts of sulphuric acid at room temperature. Subsequently the mixture is run onto ice and the precipitate filtered ofi, washed with 10% sodium chloride solution and dried. A powder is obtained which dyes wool and synthetic polyamide fibres in brilliant blue shades having good light and wet fastness properties.

EXAMPLE 21 The procedure of Example 20 is followed, employing (in place of Z-amino-l-butanol) 37 parts of Z-benzylcyclohexylamine and sulphonating the resulting dye base with 5-10% oleum. The product is a blue dye which gives dyeings of good light and wet fastness on synthetic polyamide fibres.

EXAMPLE 22 45 parts of 1-(2'-phenylaminocarbonyI-ethylamino)-4- bromanthraquinone are added to a mixture of 150 parts of 3,5,5-trimethylcyclohexylamine, 7 parts of anhydrous sodium carbonate and 0.5 part of copper-I-oxide and reacted at -135 until no further starting material is indicated. The dye base formed is isolated in the normal way and sulphonated with 7 times its amount of 3% oleum at 18-20 to yield a dye which is identical with that of Example 14.

EXAMPLE 23' 33.4 parts of 1,4-dihydroxy-S-hydroxyethylamino-8- chloroanthraquinone and 20 parts of anhydrous sodium carbonate are added to 100 parts of nitrobenzene and the temperature raised to Over the following hour 150 parts of 3,5,5-trimethylcyclohexylamine are added, the temperature being kept constant at 150-155 until no further starting material is indicated. Methanol is added to the reaction mixture at 60, on which it is cooled to 0 and the product filtered off with suction, washed with methanol and Water and dried. On sulphation in accordance with the procedure of Example 20, the product dyes wool and synthetic polyamide fibres in blue-green shades of good light and wet fastness.

EXAMPLE 24 When the 1,4-dihydroxy-S-hydroxyethylamino-S-clrloranthraquinone employed in the preceding example is replaced by 1,4-dihydroxy-5-(4-methylphenylamino)-8- chloroanthraquinone and sulphonation is carried out in 5% oleum at 2025, a dye giving blue-green dyeings is obtained.

The same dye can be arrived at by reacting 30 parts of 1,4-dihydroxy-5,8-dichloranthraquinone with 25 parts of 3,5,5-trimethylcyclohexylamine in 240 parts of nitrobenzene at 150 until the starting products are no longer indicated. The reaction mixture is then treated in the normal way and 12 parts of the isolated 1,4-dihydroxy-5- (3,5',5 trimethylcyclohexylamino) 8 chloranthraquinone are reacted with 6 parts of anhydrous sodium acetate and 75 parts of 4-methyl-l-aminobenzene at 170- 175. On completion of the reaction the dye base is sulphonated.

EXAMPLE 25 A mixture of 10 parts of 1,4-dihydroxyanthraquinone- 6-sulphonic acid, 40 parts of 3,5,S-trimethylcyclohexylamine, 70 parts of 95% ethanol, 0.8 part of zinc dust and 1.1 parts of 100% acetic acid is reacted at 80 under a nitrogen atmosphere until (after about 4 to 6 hours) no further starting material is indicated. A jet of air is then directed through the mixture to reoxidize the proportion of dye which is still in the leuco form. The dye is then isolated and purified by the normal method. It is of blue colour and gives dyeings of bright blue shade on wool and synthetic polyamide fibres which have very good light and wet fastness.

Instead of forming the leuco compound of the 1,4-dihydroxyanthraquinone-6-sulphonic acid in the reaction mixture, one can start from the pure leuco-lA-dihydroxyanthraquinone-6-sulphonic acid or from a mixture of 1,4- .dihydroxyanthraquinone-tS-sulphonic acid and its leuco compound.

In place of 95% ethanol another alcohol, e.g. n-propanol or n-butano], or an alcohol-Water mixture, e.g. 80 parts of secondary butanol and 20 parts of water, can be employed with equally good success.

EXAMPLE 26 A solution of 5.5 parts of potassium hydroxide in 200 parts of glycerol is prepared at l-110 with vigorous stirring, and 23.2 parts of sodium 1-amino-4-(3',5',5'-trimethylcyclohexylamino)-anthraquinone-2-sulphonate and 12 parts of sodium 3-nitrobenzene-l-sulphonate are added to it. The solution is reacted for 8 hours at 120125 with stirring, after which it is run into 800 parts of Water and acidified with hydrochloric acid. The product settles out and is filtered off, washed with water until of neutral reaction and dried.

10 parts of the resulting dye base are stirred in 40 parts of 100% sulphuric acid at 15 20 until a sample in completely soluble in water, on which the dye is isolated in the usual way. Its dyeings on wool and synthetic polyamide fibres are of brilliant violet shade and have good light and wet fastness.

The 23.2 parts of sodium 1-amino-4-(3,5',5'-trimethylcyclohexylamino)-anthraquinone-2-sulphonate can be replaced by 28.3 parts of the analogous 2,6-disulphonate, in which case a violet dye for wool is obtained.

EXAMPLE 27 At lO0-1l0 7.5 parts of potassium hydroxide are dissolved in 100 parts of phenol, after which 18 parts of sodium 1 amino-4-(3,5',5'-trimethylcyclohexylarnino)- anthraquinone 2 sulphonate are added. The temperature is increased to 170 and this temperature maintained until a sample is insoluble in water. The mixture is then allowed to cool to 100, 150 parts of methanol are added and it is allowed to cool further to 20. The dye base is filtered oil with suction, washed with methanol and then with water and dried. 10 parts of the dye base are entered into 45 parts of -10% oleum and stirred at 15- 25" until fully water soluble. The sulphonated dye is worked up in the normal way. On wool and synthetic polyamide fibres it gives dyeings of brilliant violet shade having good light and wet fastness.

The same dye can be obtained by reacting 16 parts of 1-amino-2-bromo 4-(3',5',5' trimethylcyclohexylamino) anthraquinone'in a mixture of 16 parts of phenol, 50 parts of nitrobenzene and 7.5 parts of potassium hydroxide at 150 until the starting products have disappeared, and continuing as stated in the foregoing.

EXAMPLE 28 A mixture of 23.2 parts of sodium 1-amino-4-(3,5,5'- trimethylcyclohexylamino)-anthraquinone 2 sulpho- I i nate, 13.5 parts of 30% sodium hydroxide solution, 100 parts of water and 22 parts of 4-rnethyl-l-mercaptobenzene is reacted for 24 hours at 95 100 with reflux. After the addition of 120 parts of ethanol the reaction mixture is allowed to cool and the product, having settled out, is filtered off, washed with ethanol and water and dried.

10 parts of the dye base thus formed are dissolved in parts of 100% sulphuric acid at 15-20. 15 parts of 25% oleum are dropped in and the the mixture is stirred until a sample is completely soluble in water. It is run onto ice and the precipitate is filtered off with suction and introduced again into 200 parts of water. The suspension is neutralized, the dye salted out, filtered oil with suction, Washed, dried and ground. It is obtained as a dark powder which gives dyeings of greenish blue shade on Wool and synthetic polyamide fibres which are fast to light and ,Wet.

treatments. I

The same dye can be obtained by reacting 11.1 par-ts of 1 amino 2 bromo 4 (3,5',5'-trimethylcyclohexylamino)-anthraquinone, 50 parts of 2 (2' methoxyethoxy)-ethanol, 2 parts of anhydrous sodium carbonate and 5 parts of 4-methyl-l-rnercaptobenezene at 80-85 until no further starting material is present, on which the product is precipitated with 40 parts of ethanol, filtered olf with suction, washed with ethanol and water and dried. It is sulphonated as described in the foregoing.

The following Table 3 details further dyes of the formula which give dyeings of greenish blue to reddish blue shade on Wool and synthetic polyamide fibres and are characterized in the table by the meanings of the substituents R14 to R18.

45 TABLE 3 Example R14 R15 Rm n m Sulpho-3Fmethylphenyl H H H H Sulpho-4-eh1orophenyl H H H H Sulpho-t-methoxyphenyl H H H H Sulpho-ZE-dimethylphenyl H H H H Sulpho-Z-methoxyphenyL H H H H Sulpho-2-methoxy-5-methyl- H H H H phenyl. Sulphophenyl OH H H OH 36- o OH H H. NH,

Sulpho4-methylphenyl. NH, H H OH- ..do NH; H H NH, ulpho--acetylaminophenyl H 01 H H 40 Sulpho-4-propionylamino- H H H H phenyl 41 Sulpho+bromophenyl H 80 11 H H 42. Sulpho-tn-butylphenyl. H S0 11 H H o H H H H 44- Sulpho+isopropylpheny H H H H 45- Sulpho-4-ethylphenyl H H H H 46 Sulpho-4-tertamylphenyl H H H H 47 Sulpho-tethoxycarbonylamino- H H H H phenyl. 48- 4-methy1phenvl H SO H H H j H SO H H H 2sulphatoethyl H H H H 2-sulphatopropyl-L H H H H 52 1-sulphatopropyl-2 H H H H 53 1-sulphatobutyl-2 H H H H at 4-sulphatobutyl-2 H H H H 55- 3-su1phato-2-hydroxyp1 y H H H H 56- ....do OH- H H OH 57 2-sulphato-propyl-L NH, H H NH; 58 2-sulphato-ethyl NH, H H OH 59 -110 H C] H H 60 d0 H H Cl H 61 4-(sulphophenyD-4-methyl- H H H H pentyl-2. 62 "do OH H H OH 63 do H SO H H H 64 4-(sulphophenyD-butyl- H H H H 65-"..- fi-(sulphophenyl)-2-rnethyl- H H H H beryl-4.

22 TABLE -3.-C0ntinued Exam- Rm ple TABLE 3.Continued Example 25 Example 19 H03S CH3 CH CH Example 20 (H) NH-CH-CH2OS H CH CH Example 21 O NH- 1 80 B I NH OH CH Example 23 EMBANH O NHz CH CH Example 24 CH CH OH; on,

Example 27 O NH; II soar:

O 3 CH Example 28 (H) NH; SOQH S CH3 CH CH Having thus disclosed the invention what We claim is: 1. Anthraquinone dye of the formula (H) NH;

Rl S 0311 R1- CH3 0 3 CH3 wherein one R stands for a hydrogen, fluorine, chlorine or bromine atom or a SO H group and the other R for a hydrogen atom, or R in each instance stands fora ch10- rine atom.

2. Anthraquinone dye according to claim 1 of the formula LORRAINE A. WEINBERGER, Primary Examiner E. I. SKELLY, Assistant Examiner US. Cl. X.R. 

